Synthesis and Structure-Activity Relationships of a Series of Aporphine Derivatives with Antiarrhythmic Activities and Acute Toxicity

Molecules. 2016 Nov 28;21(12):1555. doi: 10.3390/molecules21121555.

Abstract

Some aporphine alkaloids, such as crebanine, were found to present arrhythmic activity and also higher toxicity. A series of derivatives were synthesized by using three kinds of aporphine alkaloids (crebanine, isocorydine, and stephanine) as lead compounds. Chemical methods, including ring-opening reaction, bromination, methylation, acetylation, quaternization, and dehydrogenation, were adopted. Nineteen target derivatives were evaluated for their antiarrhythmic potential in the mouse model of ventricular fibrillation (VF), induced by CHCl₃, and five of the derivatives were investigated further in the rat model of arrhythmia, induced by BaCl₂. Meanwhile, preliminary structure-activity/toxicity relationship analyses were carried out. Significantly, N-acetamidesecocrebanine (1d), three bromo-substituted products of crebanine (2a, 2b, 2c), N-methylcrebanine (2d), and dehydrostephanine (4a) displayed antiarrhythmic effects in the CHCl₃-induced model. Among them, 7.5 mg/kg of 2b was able to significantly reduce the incidence of VF induced by CHCl₃ (p < 0.05), increase the number of rats that resumed sinus rhythm from arrhythmia, induced by BaCl₂ (p < 0.01), and the number of rats that maintained sinus rhythm for more than 20 min (p < 0.01). Therefore, 2b showed remarkably higher antiarrhythmic activity and a lower toxicity (LD50 = 59.62 mg/kg, mice), simultaneously, indicating that 2b could be considered as a promising candidate in the treatment of arrhythmia. Structural-activity analysis suggested that variationsin antiarrhythmic efficacy and toxicity of aporphines were related to the C-1,C-2-methylenedioxy group on ring A, restricted ring B structural conformation, N-quaternization of ring B, levoduction of 6a in ring C, and the 8-, 9-, 10-methoxy groups on ring D on the skeleton.

Keywords: 10,11-dibromocrebanine; 3-bromocrebanine; antiarrhythmia; aporphine derivatives; crebanine; stephanine.

MeSH terms

  • Alkaloids / adverse effects
  • Alkaloids / chemical synthesis
  • Alkaloids / pharmacology*
  • Animals
  • Anti-Arrhythmia Agents / adverse effects
  • Anti-Arrhythmia Agents / chemical synthesis
  • Anti-Arrhythmia Agents / pharmacology*
  • Aporphines / adverse effects
  • Aporphines / chemical synthesis
  • Aporphines / pharmacology*
  • Barium Compounds / toxicity
  • Carbon Tetrachloride / toxicity
  • Chlorides / toxicity
  • Disease Models, Animal
  • Drug Evaluation, Preclinical / methods
  • Female
  • Male
  • Mice
  • Rats
  • Rats, Sprague-Dawley
  • Structure-Activity Relationship
  • Tetrahydroisoquinolines / adverse effects
  • Tetrahydroisoquinolines / chemical synthesis
  • Tetrahydroisoquinolines / pharmacology
  • Ventricular Fibrillation / chemically induced
  • Ventricular Fibrillation / drug therapy*

Substances

  • Alkaloids
  • Anti-Arrhythmia Agents
  • Aporphines
  • Barium Compounds
  • Chlorides
  • Tetrahydroisoquinolines
  • barium chloride
  • crebanine
  • isocorydine
  • stephanine
  • dehydrostephanine
  • Carbon Tetrachloride